Oxide sintered body and transparent conductive oxide film

ABSTRACT

An oxide sintered body containing indium, hafnium, tantalum, and oxygen as constituent elements, in which when indium, hafnium, and tantalum are designated as In, Hf, and Ta, respectively, the atomic ratio of Hf/(In+Hf+Ta) is equal to 0.002 to 0.030, and the atomic ratio of Ta/(In+Hf+Ta) is equal to 0.0002 to 0.013.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a divisional of and claims the benefit ofpriority to U.S. application Ser. No. 16/078,488, filed Aug. 21, 2018,now U.S. Pat. No. 10,815,564, which is the National Stage of theInternational Patent Application No. PCT/JP2017/006045, filed Feb. 20,2017, which is based upon and claims the benefit of priority to JapanesePatent Application Nos. 2016-031403, filed Feb. 22, 2016, and2016-223540, filed Nov. 16, 2016. The entire contents of all of theabove applications are incorporated herein by reference.

TECHNICAL FIELD

The present invention relates to an oxide sintered body, a sputteringtarget, a transparent conductive oxide film, and a method for producingthe same.

BACKGROUND ART

Transparent conductive oxide films are utilized in the electrodes ofdisplay devices such as liquid crystal displays and of variouslight-receiving devices such as solar cells. Transparent conductiveoxide films are also utilized in various fields such as heat-rayreflective films and antistatic films for automobiles and constructionmaterials, and transparent heating devices for antifogging ofrefrigerated showcases and the like. Because those oxide films have lowresistance while having relatively high transmittance in the visiblelight region. Among these, indium oxide films containing added tin arewidely utilized as indium tin oxide (ITO) films.

In recent years, as a method for extracting device characteristics atthe maximum, it has become very important to adjust electricalcharacteristics or optical characteristics according to requirements,and optimization of physical properties in accordance particularly withvarious usage applications, including display devices such as liquidcrystal displays and solar cells, has been in active progress.

In regard to the ITO films described above, regulation of electricalcharacteristics and optical characteristics has been attempted byadjusting the amount of addition of tin. However, with this method, ithas been difficult to simultaneously improve both of electricalcharacteristics such as resistance and optical characteristics such astransmittance and light absorptivity. For example, Non-Patent Literature1 discloses the dependency of electro-optical characteristics on theamount of SnO₂ in an In₂O₃—SnO₂-based transparent conductive film.According to this, an In₂O₃—SnO₂-based transparent conductive film hasthe lowest resistance when the amount of SnO₂ is about 10 wt %. However,with such an amount of SnO₂, the plasma wavelength is shifted to theshorter wavelength side. Therefore, the absorptance is large in theinfrared region, and the transmittance decreases.

In recent years, there are many of the above-described devices having apolymer film or an organic material incorporated into the devicestructure, and therefore, it is required to reduce the maximumtemperature for the process of film-forming or device fabrication to alarge extent compared to the current processes. Thus, there is a needfor a transparent conductive film that can achieve low resistance at atemperature of 150° C. or lower, at which molecules such as liquidcrystal molecules are not decomposed and many resins and polymersubstrates can be used.

Patent Literatures 1 and 2 disclose oxide sintered bodies, each beingformed from at least one elements selected from metal elements includingindium, hafnium and tantalum, and oxygen. However, both of PatentLiteratures 1 and 2 disclose only the case in which the above-mentionedmetal elements are added singly.

Patent Literatures 3 and 4 disclose sputtering targets formed fromindium oxide containing an insulating oxide, and hafnium oxide andtantalum oxide are mentioned as examples of the insulating oxide.However, none of the literatures describes an Example of adding hafniumoxide or tantalum oxide.

CITATION LIST Patent Literature

-   Patent Literature 1: Japanese Unexamined Patent Publication No.    H9-209134-   Patent Literature 2: Japanese Unexamined Patent Publication No.    H9-150477-   Patent Literature 3: Japanese Unexamined Patent Publication No.    2003-105532-   Patent Literature 4: Japanese Unexamined Patent Publication No.    2004-149883

Non Patent Literature

-   Non-Patent Literature 1: TOSOH Research & Technology Review, 47, pp.    11-20 (2003)

SUMMARY OF INVENTION Technical Problem

An object of the present invention is to provide an oxide sintered bodyfor a transparent conductive film, the oxide sintered body being capableof achieving low resistance even on a substrate that is structurallyinseparable from an organic material or on an organic substrate during alow-temperature process at or below 150° C., a sputtering target, atransparent conductive film, and a substrate attached with the film, aswell as methods for producing those.

Solution to Problem

In view of such circumstances, the inventors of the present inventionconducted a thorough investigation, and as a result, the inventors foundthat when a particular element is added to indium oxide at a particularproportion, an oxide sintered body capable of forming a transparentconductive oxide film that realizes sufficiently low resistance in aproduction process in which the maximum temperature of a process forfilm-forming or device fabrication is suppressed to a low temperature,is obtained. Thus, the inventors completed the present invention.

That is, the present invention lies in the following items [1] to [6].

[1] An oxide sintered body having indium, hafnium, tantalum, and oxygenas constituent elements, in which when indium, hafnium, and tantalum aredesignated as In, Hf, and Ta, respectively, the atomic ratio ofHf/(In+Hf+Ta) is equal to 0.002 to 0.030, and the atomic ratio ofTa/(In+Hf+Ta) is equal to 0.0002 to 0.013.

[2] The oxide sintered body described in the above item [1], in whichthe relative density of the oxide sintered body is 97% or higher, andthe average crystal grain size is 8 μm or less.

[3] The oxide sintered body described in the above item [1] or [2], inwhich the oxide sintered body includes unavoidable impurities at aproportion of less than 1 at %.

[4] A sputtering target consisting of the oxide sintered body describedin any one of the above items [1] to [3].

[5] A method for producing a transparent conductive oxide film, themethod including sputtering using the sputtering target described in theabove item [4].

[6] A transparent conductive oxide film, in which when indium, hafnium,and tantalum are designated as In, Hf, and Ta, respectively, the atomicratio of Hf/(In+Hf+Ta) is equal to 0.002 to 0.030, and the atomic ratioof Ta/(In+Hf+Ta) is equal to 0.0002 to 0.013.

Hereinafter, suitable embodiments of the present invention will bedescribed below in detail.

The oxide sintered body of the present embodiment is such that whenindium, hafnium, and tantalum are designated as In, Hf, and Ta,respectively, the atomic ratio of Hf/(In+Hf+Ta) is equal to 0.002 to0.030, and the atomic ratio of Ta/(In+Hf+Ta) is equal to 0.0002 to0.013. The unit “at %” according to the present specification means“atomic percentage (at %)”. That is, the oxide sintered body of thepresent embodiment is such that the atomic ratio (ratio of the number ofatoms) of Hf with respect to the sum of In, Hf, and Ta is equal to 0.002to 0.030, and the atomic ratio (ratio of the number of atoms) of Ta withrespect to the sum of In, Hf, and Ta is equal to 0.0002 to 0.013.

By adopting such a composition range, a transparent conductive oxidefilm capable of realizing sufficiently low resistance in a productionprocess in which the maximum temperature of a process for film-formingor device fabrication is suppressed to a low temperature, can be formed.

From the viewpoint of being more suitable for a low-temperature process,the lower limit of Hf/(In+Hf+Ta) is preferably 0.005, and morepreferably 0.007. From the same point of view, the upper limit ofHf/(In+Hf+Ta) is preferably 0.025.

From the viewpoint of being more suitable for a low-temperature process,the lower limit of Ta/(In+Hf+Ta) is preferably 0.001, and morepreferably 0.002. From the same point of view, the upper limit ofTa/(In+Hf+Ta) is preferably 0.010.

According to the present embodiment, from the viewpoint of realizing lowresistivity of the transparent conductive oxide film at a higher level,the ratio of Hf/(In+Hf+Ta) is preferably 0.005 to 0.025.

The content of indium in the oxide sintered body of the presentembodiment is preferably 96 at % or higher, more preferably 97 at % orhigher, and even more preferably 98 at % or higher, with respect to thesum of the metal elements.

The oxide sintered body and transparent conductive oxide film of thepresent embodiment may include a very small amount of unavoidableimpurities. Examples of such impurities include compounds such as oxideshaving metal elements other than In, Hf, and Ta. The total content ofthese impurities in the oxide sintered body in terms of metal elementsis preferably 1 at % or less, more preferably 0.5 at % or less, evenmore preferably 0.1 at % or less, and particularly preferably less than0.05 at %, with respect to the sum of In, Hf, and Ta.

The relative density of the oxide sintered body of the presentembodiment is preferably 97% or higher, and more preferably 99% orhigher. In a case in which an oxide sintered body having such a relativedensity is used as a sputtering target, abnormal discharge duringsputtering can be further reduced.

The relative density of the oxide sintered body of the present inventionis calculated as follows. That is, In, Hf, and Ta are calculated interms of oxides such as In₂O₃, HfO₂, and Ta₂O₅, respectively, and theweight proportions are determined. Here, the weight proportions ofIn₂O₃, HfO₂, and Ta₂O₅ thus determined are designated as a (%), b (%),and c (%), respectively. Next, for the respective true densities, thevalues of In₂O₃: 7.18 g/cm³, HfO₂: 9.68 g/cm³, and Ta₂O₅: 8.73 g/cm³ areused to calculate the theoretical density A (g/cm³).A=(a+b+c)/((a/7.18)+(b/9.68)+(c/8.73))

The sintered density B (g/cm³) of the oxide sintered body was measuredby the Archimedean method according to JIS-R1634-1998.

The relative density (%) was determined by the following formula, as arelative value of the sintered density B (g/cm³) with respect to thetheoretical density A (g/cm³) that had been arithmetically determined.Relative density (%)=(B/A)×100

The average crystal grain size of the oxide sintered body of the presentinvention is preferably 8 μm or less, and more preferably 6 μm or less.By having such an average crystal grain size, it is possible to increasethe strength of the oxide sintered body. The lower limit of the averagecrystal grain size is preferably 0.01 μm, more preferably 0.5 μm, andeven more preferably 2 μm, from the viewpoint of the ease of production.

Meanwhile, the measurement of the average crystal grain size ofparticles in the sintered body according to the present invention iscarried out as follows. That is, the oxide sintered body of the presentinvention is cut into an appropriate size, subsequently a face to beobserved is polished on the surface, subsequently chemical etching iscarried out with a dilute hydrochloric acid solution, and the grainboundaries are clarified. For this sample, observation photographs ofthe polished surface of the sintered body are taken using EPMA, SEM/EDS,XRD, and the like. The lengths of the major axes of 500 or moreparticles in the observation photograph were determined, and thearithmetic average of the values was designated as the average crystalgrain size.

Next, a method for producing the oxide sintered body of the presentinvention will be explained.

According to the present invention, the method for mixing raw materialpowders is not particularly limited, and the method includes a mixingstep of preparing a mixed powder for molding including a powder thatserves as an indium source, a powder that serves as a hafnium source,and a powder that serves as a tantalum source; a molding step of moldingthe mixed powder and producing a molded body; and a firing step offiring the molded body and obtaining an oxide sintered body.

In the following description, the various steps will be described indetail.

In the mixing step, a mixed powder including oxides of indium, hafnium,and tantalum is produced. According to the present embodiment, themethod for mixing raw material powders is not particularly limited, anda powder that serves as an indium source, a powder that serves as ahafnium source, and a powder that serves as a tantalum source may bemixed simultaneously, or it is also acceptable to preliminarily mix someparts and then to add the remaining parts to the mixture so as to bemixed altogether.

Regarding the mixing method, a method of first preliminarily mixing apowder that serves as a hafnium source and a powder that serves as atantalum source, and calcining the mixture, is preferred. The rawmaterial powder is not particularly limited, and hafnium oxide andtantalum oxide are suitable; however, inorganic or organic salts, andthe like of hafnium and tantalum that are converted to hafnium oxide andtantalum oxide by firing can also be used. Especially in considerationof handleability, oxide powders are suitably used. The particle size ofthese powders is such that in consideration of handleability, theaverage primary particle size is preferably 1.5 μm or less, and morepreferably 0.1 μm to 1.5 μm. By using such powders, an effect ofimproving the density of the sintered body is obtained.

Here, the preliminary mixing method is not particularly limited;however, examples include mixing methods such as dry type or wet typemedium agitating mills; mediumless container rotation mixing; andmechanical agitation mixing using balls or beads of zirconia, alumina, anylon resin or the like. Specific examples include a ball mill, a beadmill, an attritor, a vibrating mill, a planetary mill, a jet mill, aV-shaped mixer, a paddle mixer, and a biaxial planetary stirring mixer.In the case of using a wet type ball mill or bead mill, an attritor, avibrating mill, a planetary mill, a jet mill, or the like, it isnecessary to dry the slurry after pulverization. This drying method isnot particularly limited; however, for example, filtration drying,fluidized bed drying, and spray drying may be mentioned as examples.Furthermore, in a case in which a metal salt solution or an alkoxidesolution is used as a raw material, a precipitate deposited from thesolution is dried. It is preferable that the preliminarily mixed powderthus obtained is calcined at 800° C. to 1,200° C. The calciningtemperature is more preferably 1,000° C. to 1,200° C., and the time issufficient with 1 hour to 3 hours. The calcined powder thus obtained issubjected to a crushing treatment or the like, and the average primaryparticle size is adjusted to 0.5 μm or less. The treatment method forcrushing or the like is not particularly limited; however, examplesinclude mixing methods such as a dry type or wet type medium agitationmill using balls or beads of zirconia, alumina, a nylon resin, or thelike. Specific examples include a ball mill, a bead mill, an attritor, avibrating mill, a planetary mill, and a jet mill. Meanwhile, in the caseof using a wet type ball mill or bead mill, an attritor, a vibratingmill, a planetary mill, a jet mill, or the like, it is necessary to drythe slurry after crushing. This drying method is not particularlylimited; however, for example, filtration drying, fluidized bed drying,and spray drying may be mentioned as examples.

Next, an indium oxide powder and the preliminarily mixed powder aremixed so as to obtain the final composition, and thus a mixed powder formolding is obtained. When an indium oxide powder is used,complicatedness of the process or ancillary works such as a powderingtreatment can be reduced. In a case in which the indium source is acompound other than oxide, for example, in a case in which the indiumsource is nitrate, chloride, or carbonate, the compound is calcined tobe converted to oxide, and the oxide is used. Regarding the particlesize of these powders, the average primary particle size is preferably1.5 μm or less, and more preferably 0.1 μm to 1.5 μm, when handleabilityis considered. By using such powders, an effect of improving the densityof the sintered body is obtained.

Here, the mixing method is not particularly limited; however, examplesinclude mixing method such as dry type or wet type medium agitationmills; mediumless container rotation mixing; and mechanical agitationmixing using balls or beads of zirconia, alumina, a nylon resin, or thelike. Specific examples include a ball mill, a bead mill, an attritor, avibrating mill, a planetary mill, a jet mill, a V-shaped mixer, a paddlemixer, and a biaxial planetary stirring mixer. Meanwhile, in the case ofusing a wet type ball mill or bead mill, an attritor, a vibrating mill,a planetary mill, a jet mill, or the like, it is necessary to dry theslurry after pulverization. This drying method is not particularlylimited; however, for example, filtration drying, fluidized bed drying,and spray drying may be mentioned as examples.

The powder thus obtained is adjusted to have an average primary particlesize of 1.5 μm or less, and more preferably 0.1 μm to 1.5 μm, and thisis used as a powder for molding. It is also possible to have theoperability in molding processes further improved by a granulationtreatment or the like. These operations provide an effect of improvingmoldability or sinterability.

In regard to the mixing step, it is preferable that the amounts of useof the powder that serves as an indium source, the powder that serves asa hafnium source, and the powder that serves as a tantalum source are inthe following ranges when the composition (final composition) of themixed powder for molding is represented by the atomic ratios of themetal elements. That is, Hf/(In+Hf+Ta) is equal to 0.002 to 0.030, andTa/(In+Hf+Ta) is equal to 0.0002 to 0.013.

By adopting such a composition range, a transparent conductive oxidefilm capable of realizing sufficiently low resistance in a productionprocess in which the maximum temperature of a process of film-forming ordevice fabrication is suppressed to a low temperature, can be formed.

In the molding step, the mixed powder for molding obtained in the mixingstep is molded. Regarding the molding method, any molding method capableof achieving molding to an intended shape can be selected asappropriate, and there are no particular limitations. For example, apress molding method and a slip casting method may be mentioned asexamples. The molding pressure can be set as appropriate to the extentthat a molded body which can be handled without having the occurrence ofcracks or the like can be produced, and there are no particularlimitations. It is preferable that the molding density of the moldedbody is as high as possible. Therefore, it is also possible to usemethods such as cold isostatic pressing (CIP). In this case, organicadditives for improving moldability may be used as necessary.

In the case of using additives at the time of molding, it is preferablethat a heating treatment is applied at a temperature of 80° C. to 500°C. before the firing step, in order to remove moisture or organicadditives remaining in the molded body. This treatment temperature maybe selected as appropriate according to the amounts and types of themoisture and additives remaining therein.

In the firing step, the molded body obtained in the molding step isfired. The rate of temperature increase is not particularly limited, andfrom the viewpoint of shortening the firing time and preventingcracking, the rate of temperature increase is preferably 10° C./hour to400° C./hour. The retention temperature for sintering (sinteringretention temperature) is preferably set to 1,400° C. or higher andlower than 1,650° C., and more preferably 1,500° C. or higher and 1,625°C. or lower. When such firing conditions are employed, an oxide sinteredbody having a higher density can be obtained. The retention time ispreferably one hour or longer, and more preferably 3 hours to 10 hours.Thereby, an oxide sintered body having a higher density and a smalleraverage crystal grain size can be obtained. The rate of temperaturedecrease is not particularly limited as long as the rate is set in anormal range, and from the viewpoint of shortening the calcination timeand preventing cracking, the rate of temperature decrease is preferably10° C./hour to 500° C./hour.

The atmosphere at the time of firing is preferably an atmospherecontaining oxygen. It is particularly preferable that firing isperformed under an oxygen gas stream. Particularly, it is preferablethat the ratio of the oxygen flow rate (L/min) at the time ofintroducing oxygen into the furnace upon sintering and the weight of themolded body (input amount, kg) (weight of molded body/oxygen flow rate)is adjusted to 1.0 [kg/(L/min)] or less. In this way, an oxide sinteredbody having a higher density can be obtained.

The method for producing the oxide sintered body of the presentinvention is not limited to the above-described method. For example, inthe mixing step, a mixed powder for molding may be prepared bycollecting and mixing a powder that serves as an indium source, a powderthat serves as a hafnium source, and a powder that serves as a tantalumsource, without performing preliminary mixing and calcining.

The sputtering target of the present embodiment consists of the oxidesintered body described above. Since such a sputtering target hasexcellent discharge characteristics at the time of film-forming,abnormal discharge is suppressed, and film-forming can be carried outstably. This sputtering target has a composition and a structure similarto those of the oxide sintered body.

According to the present embodiment, the oxide sintered body may be useddirectly as a sputtering target, or the oxide sintered body may be usedas a sputtering target after being processed into a predetermined shape.

The surface roughness of the sputtering surface of the sputtering targetis, as the center line average roughness (Ra), preferably 3 μm or less,and more preferably 2 μm or less. Thereby, the number of times ofabnormal discharge at the time of film-forming can be furthersuppressed, and stable film-forming can be carried out. The center lineaverage roughness can be adjusted by, for example, a method ofsubjecting the surface of a composite oxide sintered body that serves asthe sputtering surface to mechanical processing with grinding wheels ofdifferent mesh sizes, or a method of spray processing with a sandblastor the like. The center line average roughness can be determined by, forexample, evaluating the surface to be measured, using a surface propertyanalyzer.

A film can be formed by a sputtering method using the sputtering targetof the present embodiment. Regarding the sputtering method, a DCsputtering method, an RF sputtering method, an AC sputtering method, aDC magnetron sputtering method, an RF magnetron sputtering method, anion beam sputtering method, or the like can be selected as appropriate.Among these, a DC magnetron sputtering method and an RF magnetronsputtering method are preferred from the viewpoint that film-forming canbe achieved uniformly in a large-sized area at a high speed.

The temperature at the time of sputtering is not particularly limited;however, the temperature is set as appropriate according to the heatresistance of the substrate used. For example, in the case of usingalkali-free glass as a substrate, usually, the temperature is preferablyset to 250° C. or lower, and in the case of using a film made of a resinas a substrate, usually, the temperature is preferably set to 150° C. orlower. In the case of using a substrate having excellent heatresistance, such as quartz, a ceramic, or a metal, it is also possibleto form a film at a temperature higher than or equal to thesetemperatures.

Regarding the atmospheric gas at the time of sputtering, usually, aninert gas, for example, argon gas, is used. If necessary, oxygen gas,nitrogen gas, hydrogen gas, or the like may also be used.

The transparent conductive oxide film of the present embodiment can beobtained by forming a film by sputtering using the sputtering targetdescribed above. That is, the transparent conductive oxide film of thepresent embodiment can be obtained by carrying out a process of forminga film by sputtering a sputtering target consisting of an oxide sinteredbody.

The transparent conductive oxide film of the present embodiment canrealize sufficiently lower resistance even in a production process inwhich the maximum temperature of a process for film-forming or devicefabrication is suppressed to a low temperature such as a temperaturebelow 200° C., and particularly below 180° C. Furthermore, a transparentconductive oxide film having excellent durability in a high-temperatureor high-humidity environment can be obtained.

Regarding the composition of a transparent conductive oxide film that isobtainable by the method described above, the composition of the targetused for sputtering is reflected. That is, by using a sputtering targetformed from the oxide sintered body described above, a transparentconductive oxide film having a composition in which Hf/(In+Hf+Ta) isequal to 0.002 to 0.030, and Ta/(In+Hf+Ta) is equal to 0.0002 to 0.013,is obtained.

That is, the transparent conductive oxide film of the present embodimenthas a composition similar to the compositions of the sputtering targetand the oxide sintered body.

Therefore, the transparent conductive oxide film contains an oxidehaving indium, hafnium, tantalum, and oxygen as constituent elements.Preferred ranges of the content of indium, the content of hafnium, andthe content of tantalum in the transparent conductive oxide film aresimilar to those of the oxide sintered body.

From the viewpoint that sufficiently low resistance can be realized in aproduction process in which the maximum temperature of a process forfilm-forming of the transparent conductive oxide film of the presentembodiment or device fabrication is suppressed to a low temperature, thelower limit of the ratio of Hf/(In+Hf+Ta) is preferably 0.005, and morepreferably 0.007. From a similar viewpoint, the upper limit of the ratioof Hf/(In+Hf+Ta) is preferably 0.025, and more preferably 0.021.

From the viewpoint that sufficiently low resistance can be realized in aproduction process in which the maximum temperature of a process forfilm-forming of the transparent conductive oxide film of the presentembodiment or device fabrication is suppressed to a low temperature, thelower limit of the ratio of Ta/(In+Hf+Ta) is preferably 0.001, and morepreferably 0.003. From a similar viewpoint, the upper limit of the ratioof Ta/(In+Hf+Ta) is preferably 0.010.

According to the present embodiment, from the viewpoint of realizing lowresistivity of the transparent conductive oxide film at a higher level,the ratio of Hf/(In+Hf+Ta) is preferably 0.005 to 0.025. Furthermore,the ratio of Ta/(In+Hf+Ta) is preferably 0.001 to 0.010.

The transparent conductive oxide film is used in a form having anappropriate film thickness according to the usage application. Forexample, when the transparent conductive oxide film is used as anelectrode for various light-receiving devices such as a solar cell; aTFT or CF of a display device; a transparent electrode of an organic ELdevice; or the like, a transparent conductive oxide film having a filmthickness of about 100 nm to 300 nm is used in many cases. In usageapplications in a display device such as a liquid crystal display, orparticularly a touch panel, a flexible substrate that uses a polymerfilm is employed in many cases, in addition to a glass substrate. Insuch usage applications, the transparent conductive oxide film is usedas a very thin film having a film thickness of about 5 nm to 50 nm.Furthermore, due to have a structure having a material with low heatresistance laminated thereon or to use a polymer film, it is requiredthat the maximum temperature of the film-forming process is suppressedto a low temperature.

The transparent conductive oxide film of the present invention can besuitably used as a laminated substrate including a substrate and thetransparent conductive oxide film thus configured.

Here, examples of the substrate include a glass substrate includingalkali-free glass, quartz or the like; a polymer film substrate made ofa resin; and a substrate of a ceramic or a metal. Particularly, in thecase of being used for display devices, since visibility is extremelyimportant, a glass substrate containing alkali-free glass or quartz, ora polymer film substrate made of a resin is suitable.

Such a laminated substrate is suitably used as a device configured toinclude a plurality of functional components. For example, the laminatedsubstrate is suitable for an optical device such as a solar cell, or adisplay device such as an FPD or a touch panel. Particularly, thedisplay devices mentioned above are incorporated into electronicequipment and suitably used, and are particularly suitable forsmall-sized high-performance electronic equipment such as mobileequipment.

Thus, suitable embodiments of the present invention have been described;however, the present invention is not intended to be limited to theabove-described embodiments.

Advantageous Effects of Invention

The oxide sintered body of the present invention can be used as asputtering target. By sputtering using the target, the transparentconductive oxide film of the present invention can be produced whileabnormal discharge during sputtering is suppressed. Since thetransparent conductive oxide film of the present invention can achievevery low resistivity such as 300 μΩ·cm even at a process temperature of150° C. or lower, generally the production processes for electronicdevices are facilitated, and also, the transparent conductive oxide filmcan be suitably used in devices that use organic substrates or inorganic semiconductor devices.

EXAMPLE

The present invention will be described more specifically by referringto the following Examples; however, the present invention is notintended to be limited to these Examples.

Examples 1 to 20

Sintered bodies, sputtering targets, and transparent conductive filmswere produced according to the compositions indicated in Table 1 by thefollowing methods.

<Production of Oxide Sintered Body>

As raw material powders, an indium oxide powder having a purity of99.99% by weight and an average particle size of 0.5 μm, a hafnium oxidepowder having a purity of 99.9% by weight and an average particle sizeof 0.2 μm, and a tantalum oxide powder having a purity of 99.9% byweight and an average particle size of 0.2 μm were prepared. These rawmaterial powders were weighed so as to obtain the atomic ratio describedin Table 1, the powders were mixed in a dry type ball mill, and thus amixed powder for molding was obtained. The average particle size of themixed powder was 0.2 μm.

This mixed powder was molded by the following procedure, and a moldedbody was produced. First, the mixed powder was molded using a moldhaving a diameter of 150 mm by applying pressure at 0.3 ton/cm². Next,CIP molding of applying pressure at 3.0 ton/cm² was performed, and thusa cylindrical-shaped molded body was obtained. This molded body wasdisposed in a sintering furnace conditioned to have a pure oxygenatmosphere, and the molded body was sintered under the followingconditions. Thus, a disc-shaped oxide sintered body was produced. Inthis manner, the oxide sintered bodies of the various Examples, variousComparative Examples, and various Reference Examples were obtained. Theretention time is the time for which the molded body was maintained atthe sintering retention temperature.

(Firing Conditions)

-   -   Rate of temperature increase: 50° C./hour    -   Sintering retention temperature: 1,600° C.    -   Retention time: 5 hours    -   Sintering atmosphere: From before the initiation of temperature        increase (room temperature) to the temperature reached 100° C.        upon temperature decrease, pure oxygen gas was introduced into        the furnace.    -   Rate of temperature decrease: 100° C./hour    -   Weight of molded body/oxygen flow rate: 0.9 [kg/(L/min)]

<Evaluation of Oxide Sintered Body>

(Composition)

The compositions of the oxide sintered bodies of the various Examples,various Comparative Examples, and various Reference Examples werequantitatively determined by ICP emission spectrometry using acommercially available ICP emission spectrometer. Then, the atomic ratiowas determined. The results are shown in Table 1.

Meanwhile, the compositions of the oxide sintered bodies wererespectively almost identical with the compositions of the mixed powdersfor molding.

(Relative Density)

The relative densities of the oxide sintered bodies of the variousExamples, various Comparative Examples, and various Reference Exampleswere determined. The relative density is a value that is determined bythe following formula, when the theoretical density of the oxidesintered body is designated as A and the sintered density is designatedas B. The methods for measuring the theoretical density A and thesintered density B are as described above. The measurement results areshown in Table 1.Relative density (%)=(B/A)×100

(Average Crystal Grain Size)

The average crystal grain sizes of the crystal grains that constitutedthe oxide sintered bodies of the various Examples, various ComparativeExamples, and various Reference Examples were measured. The method formeasuring the average crystal grain size is as described above. However,an observation photograph (magnification ratio: 1,000 to 5,000 times) ofa polished surface of an oxide sintered body was taken using a scanningelectron microscope. In this observation photograph, the lengths of themajor axes of 500 particles were determined. The arithmetic mean lengthof the major axes thus determined was designated as the average crystalgrain size. The measurement results are shown in Table 1.

(Three-Point Flexural Strength)

Regarding the strength of a sintered body, the three-point flexuralstrength was measured according to JIS-R-1601.

<Production of Sputtering Target and Transparent Conductive Oxide Film>

The oxide sintered bodies produced in the various Examples, variousComparative Examples, and various Reference Examples were processed intoa disc shape (diameter: 4 inches=101.6 mm) The surface that will beserved as a sputtering surface when the oxide sintered body was used asa sputtering target was polished using a flat surface grinding machineand a diamond grinding wheel. The center line average roughness (Ra) wasadjusted by changing the mesh size of the grinding wheel at the time ofpolishing. In this manner, a sputtering target was produced. Ra of thesputtering surface of the sputtering target thus produced was measuredusing a commercially available surface property analyzer (apparatusname: SURFTEST SV-3100, manufactured by Mitutoyo Corporation). Theresults were as shown in Table 1.

A film was formed on a substrate under the following conditions by a DCmagnetron sputtering method using the sputtering target thus obtained.After the film-forming, a post-treatment was carried out under thefollowing conditions, and a transparent conductive oxide film wasobtained.

(Film-Forming Conditions)

-   -   Apparatus: DC magnetron sputtering apparatus    -   Magnetic field intensity: 1,000 Gauss (right above the target,        horizontal component)    -   Substrate temperature: Room temperature (25° C.)    -   Attained degree of vacuum: 8×10⁻⁵ Pa    -   Atmosphere at the time of film-forming: Argon    -   Gas pressure at the time of sputtering: 0.5 Pa    -   DC power: 200 W    -   Film thickness: 30 nm    -   Substrate used: Alkali-free glass (EAGLE XG glass manufactured        by Corning Incorporated, thickness: 0.7 mm)

(Post-Treatment Conditions after Film-Forming)

After the film-forming, the transparent conductive film-attachedsubstrate was subjected to a heat treatment of heating for 60 minutes at150° C. in air. The rate of temperature increase at this time was set to50° C./min.

<Evaluation of Transparent Conductive Oxide Film>

(Film Thickness)

The thickness of the thin film was measured using DEKTAK 3030(manufactured by Sloan Technology Corp.).

(Resistivity)

The resistivity of the thin film was measured using HL5500 (manufacturedby Japan Bio-Rad Laboratories, Inc.).

(Light Transmittance)

The light transmittance of a sample having a transparent conductiveoxide film formed on a substrate was measured using a spectrophotometer(trade name: U-4100, manufactured by Hitachi High-TechnologiesCorporation) in a wavelength range of from 240 nm to 2,600 nm, and theaverage value of the light transmittances at a wavelength of 400 nm to800 nm, which is important for display devices, was determined.

The measurement results for the resistivity and the light transmittanceof the transparent conductive films thus obtained are shown in Table 1.

Comparative Examples 1 to 10

Sintered bodies, sputtering targets, and transparent conductive filmswere produced by methods similar to those used in Examples 1 to 20,according to the compositions indicated in Table 1.

Reference Example 1

A sintered body, a sputtering target, and a transparent conductive filmwere produced according to the composition indicated in Table 1 bymethods similar to those used in Examples 1 to 20, except that theretention time during firing was set to 15 hours.

Reference Example 2

A sintered body, a sputtering target, and a transparent conductive filmwere produced according to the composition indicated in Table 1 bymethods similar to those used in Examples 1 to 20, except that theretention time during firing was set to 25 hours.

The measurement results are shown in Table 1.

TABLE 1 Final composition of Average Three- Light powder and compositionRelative crystal point transmittance in of sintered body density ofgrain size of flexural Ra of Annealing wavelength range Hf/(In +Ta/(In + sintered body sintered body strength target temperatureResistivity of 400 to 800 nm Hf + Ta) Hf + Ta) (%) (μm) (MPa) (μm) (°C.) (μΩ · cm) (%) Example 1 0.0110 0.0012 99.2 5.2 195 0.42 150 259 88.0Example 2 0.0157 0.0018 99.2 5.2 196 0.48 150 233 88.2 Example 3 0.01200.0018 99.2 5.6 190 0.47 150 253 88.3 Example 4 0.0150 0.0015 99.1 5.2191 0.47 150 231 88.4 Example 5 0.0160 0.0018 99.1 5.3 191 0.42 150 23788.4 Example 6 0.0200 0.0022 99.1 5.2 193 0.42 150 268 88.3 Example 70.0180 0.0017 99.1 5.1 196 0.42 150 260 88.1 Example 8 0.0235 0.001899.2 5.4 189 0.42 150 279 87.5 Example 9 0.0235 0.0018 99.2 5.2 190 0.42150 273 87.3 Example 10 0.0072 0.0018 99.3 5.7 189 0.42 150 266 88.4Example 11 0.0072 0.0035 99.4 4.8 200 0.45 150 284 88.3 Example 120.0055 0.0010 99.1 3.5 280 0.41 150 299 88.4 Example 13 0.0280 0.005099.3 5.2 189 0.42 150 294 87.3 Example 14 0.0235 0.0033 99.3 5.0 1930.43 150 282 87.3 Example 15 0.0150 0.0040 99.3 5.2 189 0.42 150 22487.0 Example 16 0.0148 0.0050 99.3 4.8 200 0.42 150 226 87.0 Example 170.0190 0.0060 99.3 5.0 203 0.45 150 218 87.3 Example 18 0.0190 0.007099.3 4.2 230 0.42 150 220 86.9 Example 19 0.0190 0.0093 99.3 4.5 2120.42 150 214 85.9 Example 20 0.0170 0.0090 99.3 4.9 204 0.42 150 21286.3 Comparative 0.0320 0.0018 99.0 5.3 190 0.47 150 314 87.2 Example 1Comparative 0.0240 0.0140 99.4 4.8 200 0.42 150 362 87.4 Example 2Comparative 0.0004 0.0010 99.1 5.3 189 0.45 150 462 88.8 Example 3Comparative 0.0310 0.0080 99.2 5.9 178 0.42 150 518 87.2 Example 4Comparative 0.0070 — 98.8 4.9 200 0.38 150 345 88.2 Example 5Comparative 0.0120 — 99.1 5.5 189 0.38 150 301 87.5 Example 6Comparative 0.0300 — 99.1 5.2 200 0.40 150 309 86.4 Example 7Comparative — 0.0020 99.3 5.3 192 0.41 150 441 88.4 Example 8Comparative — 0.0145 98.8 5.1 198 0.40 150 323 87.5 Example 9Comparative — 0.0230 99.0 5.1 203 0.40 150 385 87.4 Example 10 Reference0.0150 0.0040 99.8 9.0 110 0.40 150 227 87.4 Example 1 Reference 0.01900.0050 99.8 15.0 96 0.40 150 227 87.4 Example 2

Reference Example 3

A sintered body, a sputtering target, and a transparent conductive filmwere produced by methods similar to those used in Examples 1 to 20,except that the additive element was changed to Sn. The evaluationresults are shown in Table 2. From these results, it is understood thatthe present invention can achieve low resistance at a low-temperatureprocess, even when compared to In₂O₃ (ITO) having added Sn, which iscurrently generally used.

TABLE 2 Final composition of Average Three- Light powder and compositionRelative crystal point transmittance in of sintered body density ofgrain size of flexural Ra of Annealing wavelength range Additivesintered body sintered body strength target temperature Resistivity of400 to 800 nm element M M/(In + M) (%) (μm) (MPa) (μm) (° C.) (μΩ · cm)(%) Reference Sn 0.0270 99.0 3.9 215 0.42 150 331 86.7 Example 3

The present invention has been explained in detail with reference toparticular embodiments; however, it is clearly known to those havingordinary skill in the art that various modifications or corrections canbe added without deviating from the essence and scope of the presentinvention.

Meanwhile, the entire disclosures of the specifications, claims,drawings, and abstracts of Japanese Patent Application No. 2016-031403,filed on Feb. 22, 2016, and Japanese Patent Application No. 2016-223540,filed on Nov. 16, 2016, are incorporated herein by reference asdisclosures of the specification of the present invention.

INDUSTRIAL APPLICABILITY

According to the present invention, a sputtering target and an oxidesintered body that is suitably used as a sputtering target can beprovided. By sputtering using the sputtering target, a transparentconductive oxide film can be produced while target damage duringfilm-forming is suppressed. The transparent conductive oxide film of thepresent invention can realize low resistance in a production process inwhich the maximum temperature of a process for film-forming of thetransparent conductive oxide film or device fabrication is suppressed toa low temperature. Therefore, for example, when the transparentconductive oxide film is used in a solar cell, optical losses and heatgeneration caused by light absorption can be suppressed compared toconventional cases. Furthermore, since the transparent conductive oxidefilm of the present invention has low resistivity and high transmittancewhen produced in a low-temperature film-forming process, the transparentconductive oxide film can be suitably used in touch panel applicationswhere flexible substrates such as films are used, in addition to glasssubstrates. Furthermore, since the transparent conductive oxide film ofthe present invention has high durability, the transparent conductiveoxide film can be suitably used for various device usage applications.

The invention claimed is:
 1. A transparent conductive oxide film,comprising: an oxide including indium, hafnium, tantalum, and oxygen asconstituent elements, wherein the oxide satisfies that an atomic ratioof Hf/(In+Hf+Ta) is equal to 0.002 to 0.030, and that an atomic ratio ofTa/(In+Hf+Ta) is equal to 0.0002 to 0.013, where In, Hf and Ta areindium, hafnium, and tantalum, respectively.
 2. The transparentconductive oxide film according to claim 1, wherein the atomic ratio ofHf/(In+Hf+Ta) is equal to 0.005 to 0.025.
 3. The transparent conductiveoxide film according to claim 1, wherein the atomic ratio ofHf/(In+Hf+Ta) is equal to 0.007 to 0.021.
 4. The transparent conductiveoxide film according to claim 1, wherein the atomic ratio ofTa/(In+Hf+Ta) is equal to 0.001 to 0.010.
 5. The transparent conductiveoxide film according to claim 1, wherein the atomic ratio ofTa/(In+Hf+Ta) is equal to 0.003 to 0.010.
 6. The transparent conductiveoxide film according to claim 1, wherein the atomic ratio ofHf/(In+Hf+Ta) is equal to 0.005 to 0.025, and the atomic ratio ofTa/(In+Hf+Ta) is equal to 0.001 to 0.010.